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CN114505055A - Sludge-based biochar, preparation method and application thereof in aspect of carbon dioxide adsorption - Google Patents

Sludge-based biochar, preparation method and application thereof in aspect of carbon dioxide adsorption Download PDF

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CN114505055A
CN114505055A CN202210150310.6A CN202210150310A CN114505055A CN 114505055 A CN114505055 A CN 114505055A CN 202210150310 A CN202210150310 A CN 202210150310A CN 114505055 A CN114505055 A CN 114505055A
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sludge
based biochar
carbon dioxide
acid
biochar
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CN114505055B (en
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张志远
张力琳
王许涛
周恒涛
鞠睿
饶培军
朱焕光
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Henan University of Urban Construction
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    • B01J20/3475Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • CCHEMISTRY; METALLURGY
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Abstract

The invention relates to the technical field of sludge-based biochar, in particular to sludge-based biochar, a preparation method and application thereof in the aspect of adsorbing carbon dioxide. According to the invention, a proper amount of rice hulls are mixed into activated sludge with high water content for hydrothermal carbonization to prepare the sludge-based biochar, the specific surface area and the microporous structure of the sludge-based biochar are improved by means of the supporting effect of the rice hulls in the carbonization process, and the sludge-based biochar is further subjected to acid washing activation and amino modification to ensure that the carbon dioxide adsorption capacity of the sludge-based biochar is stronger, so that the sludge-based biochar has extremely high adsorption capacity and adsorption efficiency when the carbon dioxide in flue gas is adsorbed.

Description

一种污泥基生物炭、制备方法及其在吸附二氧化碳方面的 应用Sludge-based biochar, preparation method and application thereof in adsorbing carbon dioxide

技术领域technical field

本发明涉及污泥基生物炭技术领域,具体涉及一种污泥基生物炭、制备方法及其在吸附二氧化碳方面的应用。The invention relates to the technical field of sludge-based biochar, in particular to a sludge-based biochar, a preparation method and its application in adsorbing carbon dioxide.

背景技术Background technique

二氧化碳(CO2)作为主要的温室气体之一,在大气层中的浓度逐年增高,加剧了全球变暖的趋势。诸多减少CO2排放的技术和方法中,CO2捕集、利用与封存技术(CarbonCapture,Utilization and Storage,CCUS)现阶段被认为是控制大气层CO2浓度以减缓气候变化最有效的途径。CCUS技术是指将CO2从能源利用过程的排放源中分离并进行捕集,然后作为原料进行工业和农业转化利用,或运输到适宜的场地进行封存,实现CO2与大气长期隔离的技术体系。然而,不管是对CO2的转化利用,还是封存固定,对其捕获都是必要的前提。As one of the main greenhouse gases, carbon dioxide (CO 2 ) has an increasing concentration in the atmosphere year by year, aggravating the trend of global warming. Among the many technologies and methods to reduce CO 2 emissions, CO 2 capture, utilization and storage technology (Carbon Capture, Utilization and Storage, CCUS) is currently considered to be the most effective way to control atmospheric CO 2 concentration to mitigate climate change. CCUS technology refers to a technical system that separates and captures CO 2 from the emission source in the energy utilization process, and then uses it as a raw material for industrial and agricultural conversion, or transports it to a suitable site for storage to achieve long-term isolation of CO 2 from the atmosphere. . However, whether it is the conversion and utilization of CO2 , or sequestration and immobilization, its capture is a necessary prerequisite.

多孔炭材料孔隙结构发达、比表面积高、热化学稳定性良好、易于再生且具有较强的可调控性,在CO2吸附领域具有广阔的应用前景,但是由于制备成本较高而限制了实际应用。将生物质在高温环境下进行热裂解可以得到固态生物炭产物,生物炭具有一定的吸附能力,并且成本相对较低。而当以废弃物为原料制备生物炭时,相比常规的生物质具有更大的经济优势。因此,以废弃物为原料开发CO2吸附性能优良的生物炭,不仅能够降低生产成本,还具有重要的环保意义和实用价值。Porous carbon materials have developed pore structure, high specific surface area, good thermochemical stability, easy regeneration, and strong controllability. They have broad application prospects in the field of CO adsorption, but their practical application is limited due to the high preparation cost. . Thermal cracking of biomass in a high temperature environment can obtain solid biochar products. Biochar has a certain adsorption capacity and relatively low cost. When biochar is prepared from waste as raw material, it has greater economic advantages than conventional biomass. Therefore, using waste as raw material to develop biochar with excellent CO adsorption performance can not only reduce the production cost, but also have important environmental significance and practical value.

污泥是污水处理过程中沉降下来的粘稠絮凝体,其中含有大量的重金属、虫卵、病原体和有机污染物,对环境具有严重的危害性。污泥中碳元素含量较高,具有制备污泥基生物炭的基本条件。污泥基生物炭(Sludge-Derived Biochar,SDBC)制备工艺主要包括热裂解和活化两个部分,将污泥在无氧或缺氧环境下进行高温热裂解,促进孔隙结构形成和炭化程度增加,在此过程中或在后期辅以有效的物理或化学活化处理方式,进一步有针对性地提高污泥基生物炭的孔隙结构、比表面积、吸附特性和选择分离特性等。该工艺不仅能够降低污泥容积、杀死虫卵和病原体、钝化污泥中重金属,还可以得到气态可燃气和液态焦油作为能源使用。此外,污泥中重金属含量较高,不仅在制备过程中能起到催化作用,还能使污泥基生物炭表面产生丰富的含氧官能团(-COOMe和-OMe,Me表示金属原子),进而增强吸附性能。但是污泥基生物炭应用于CO2吸附领域的相关研究较少,且研究成果并不理想,对烟道温度下混合气体的CO2选择性吸附研究更为鲜见,因此提供一种能够用于吸附烟气中二氧化碳的污泥基水泥生物炭具有极大的经济意义。Sludge is a viscous floc that settles down in the sewage treatment process, which contains a large amount of heavy metals, eggs, pathogens and organic pollutants, which is seriously harmful to the environment. The content of carbon elements in sludge is high, and it has the basic conditions for preparing sludge-based biochar. The preparation process of Sludge-Derived Biochar (SDBC) mainly includes two parts: thermal cracking and activation. The sludge is pyrolyzed at high temperature in an anaerobic or anoxic environment to promote the formation of pore structure and increase the degree of carbonization. In this process or in the later stage, effective physical or chemical activation treatment methods are used to further improve the pore structure, specific surface area, adsorption characteristics and selective separation characteristics of sludge-based biochar. This process can not only reduce sludge volume, kill insect eggs and pathogens, passivate heavy metals in sludge, but also obtain gaseous combustible gas and liquid tar for energy use. In addition, the high content of heavy metals in sludge can not only play a catalytic role in the preparation process, but also generate abundant oxygen-containing functional groups (-COOMe and -OMe, Me means metal atoms) on the surface of sludge-based biochar, and then Enhanced adsorption performance. However, there are few relevant studies on the application of sludge-based biochar in the field of CO 2 adsorption, and the research results are not ideal. Sludge-based cement biochar for adsorption of carbon dioxide in flue gas has great economic significance.

发明内容SUMMARY OF THE INVENTION

基于上述内容,本发明的目的在于提供一种污泥基生物炭、制备方法及其在吸附二氧化碳方面的应用。通过将在污泥中混入适量稻壳进行热解炭化制备污泥基生物炭,借助稻壳在碳化过程中的支撑作用,提高污泥基生物炭的比表面积和微孔结构,借助酸洗活化和氨基改性的方法从而使其二氧化碳的吸附能力更强。Based on the above content, the purpose of the present invention is to provide a sludge-based biochar, a preparation method and its application in adsorbing carbon dioxide. The sludge-based biochar is prepared by mixing an appropriate amount of rice husk into the sludge for pyrolysis and carbonization. With the support of the rice husk in the carbonization process, the specific surface area and microporous structure of the sludge-based biochar are improved. And amino modification method to make its carbon dioxide adsorption capacity stronger.

本发明的技术方案之一,一种污泥基生物炭,以污泥和稻壳的混合物为原料,进行水热炭化,然后经过酸洗活化和氨基改性得到。One of the technical solutions of the present invention is a sludge-based biochar, which is obtained by using a mixture of sludge and rice husks as raw materials, performing hydrothermal carbonization, and then undergoing acid washing activation and amino modification.

进一步地,所述污泥的干重和稻壳的混合质量比为10:(2-4)。Further, the mixed mass ratio of the dry weight of the sludge to the rice husk is 10:(2-4).

本发明的技术方案之二,上述污泥基生物炭的制备方法,包括以下步骤:The second technical solution of the present invention, the preparation method of the above-mentioned sludge-based biochar, comprises the following steps:

(1)将污泥和稻壳混合得到混合物进行水热炭化得到碳化产物;(1) mixing sludge and rice husks to obtain a mixture for hydrothermal carbonization to obtain a carbonized product;

(2)碳化产物首先置于酸溶液中进行浸渍,然后置于有机胺溶液中浸渍,然后真空干燥得到所述污泥基生物炭。(2) The carbonized product is first impregnated in an acid solution, then impregnated in an organic amine solution, and then vacuum-dried to obtain the sludge-based biochar.

进一步地,所述步骤(1)中,水热炭化条件:温度120℃—220℃,时间0.5—2h。Further, in the step (1), the hydrothermal carbonization conditions: the temperature is 120°C-220°C, and the time is 0.5-2h.

进一步地,所述水热反应的料液比为1g:5-10mL。Further, the material-to-liquid ratio of the hydrothermal reaction is 1 g: 5-10 mL.

进一步地,所述步骤(2)中,所述酸溶液的溶质为盐酸、磷酸、醋酸、柠檬酸、氢氟酸中的一种或多种,溶剂为去离子水,浓度为0.5—2mol/L,浸渍时间为2—6h,温度40℃—60℃;所述有机胺溶液的溶质为乙二胺、乙醇胺、二乙醇胺、三乙胺、乙胺,溶剂为乙醇,有机胺溶液浓度为5-15wt%,浸渍时间为6-12h。Further, in the step (2), the solute of the acid solution is one or more of hydrochloric acid, phosphoric acid, acetic acid, citric acid, and hydrofluoric acid, the solvent is deionized water, and the concentration is 0.5-2mol/ L, the immersion time is 2-6h, the temperature is 40°C-60°C; the solute of the organic amine solution is ethylenediamine, ethanolamine, diethanolamine, triethylamine, ethylamine, the solvent is ethanol, and the concentration of the organic amine solution is 5 -15wt%, immersion time is 6-12h.

进一步地,所述步骤(1)中,所述混合物在水热炭化前进行以下预处理:慢速搅拌混匀后快速搅拌3-5h,微波超声预处理10—20min。Further, in the step (1), the mixture is subjected to the following pretreatments before hydrothermal carbonization: stirring at a slow speed, followed by rapid stirring for 3-5 hours, and microwave ultrasonic pretreatment for 10-20 minutes.

进一步地,所述慢速搅拌转速为100-150r/min,所述快速搅拌转速500-600r/min,微波超声预处理温度100℃—250℃,超声频率300-500Hz。Further, the slow stirring speed is 100-150 r/min, the fast stirring speed is 500-600 r/min, the microwave ultrasonic pretreatment temperature is 100-250 °C, and the ultrasonic frequency is 300-500 Hz.

进一步地,所述混合物在进行微波超声预处理前进行以下预处理:40-50℃条件下厌氧发酵3-5天,慢速搅拌混匀后快速搅拌3-5h。所述慢速搅拌转速为100-150r/min,所述快速搅拌转速500-600r/min。Further, the mixture is subjected to the following pretreatment before microwave ultrasonic pretreatment: anaerobic fermentation at 40-50° C. for 3-5 days, slow stirring and mixing, and rapid stirring for 3-5 hours. The slow stirring speed is 100-150 r/min, and the fast stirring speed is 500-600 r/min.

本发明的技术方案之三,上述污泥基生物炭在吸附二氧化碳方面的应用。The third technical solution of the present invention is the application of the above-mentioned sludge-based biochar in adsorbing carbon dioxide.

进一步地,所述污泥基生物炭在吸附燃烧后烟气中二氧化碳中的应用。Further, the application of the sludge-based biochar in adsorbing carbon dioxide in flue gas after combustion.

与现有技术相比,本发明的有益效果:Compared with the prior art, the beneficial effects of the present invention:

污泥和稻壳均属于废弃物,稻壳透气性好,密度低,和污泥混合能够降低污泥的密实度,在进行热解炭化过程中,起到支撑作用,从而增加污泥基生物炭的孔隙结构和比表面积;同时碳化过程中污泥和稻壳中的重金属、碱金属等成分会相互反应,从而有利于进一步提高污泥基生物炭的二氧化碳吸附能力。Sludge and rice husk are both wastes. Rice husk has good air permeability and low density. Mixing with sludge can reduce the compactness of sludge. The pore structure and specific surface area of carbon; at the same time, heavy metals, alkali metals and other components in sludge and rice husks will react with each other during the carbonization process, which is beneficial to further improve the carbon dioxide adsorption capacity of sludge-based biochar.

污泥基生物炭的炭热解炭化采用水热炭化法,与传统热解炭化法相比,水热炭化在水环境中进行,受污泥含水率的影响小,无需进行预脱水干燥处理。所需反应温度低,能耗小,不易产生二次污染的优势,并且获得的生物炭产率和含碳量高,官能团丰富。The carbon pyrolysis carbonization of sludge-based biochar adopts the hydrothermal carbonization method. Compared with the traditional pyrolysis carbonization method, the hydrothermal carbonization is carried out in the water environment, which is less affected by the moisture content of the sludge and does not need to be pre-dehydrated and dried. The required reaction temperature is low, the energy consumption is small, and the advantages of secondary pollution are not easily generated, and the obtained biochar has high yield and carbon content, and is rich in functional groups.

经水热炭化后进行酸洗活化,脱除污泥基生物炭表面的灰分,增加生物炭表面积、孔体积和表面官能团的数量。经酸洗活化后再进行氨基改性,在产生的污泥生物炭表面引入氨基基团,胺类化合物可很好地捕获二氧化碳,二氧化碳分子能够和伯胺、仲胺发生化学反应形成氨基甲酸酯类物质,促进二氧化碳的吸附,从而进一步提高污泥基生物炭对二氧化碳的选择性吸附能力。After hydrothermal carbonization, pickling activation is performed to remove ash on the surface of sludge-based biochar and increase the surface area, pore volume and number of surface functional groups of biochar. After acid washing and activation, amino group modification is carried out, and amino groups are introduced on the surface of the produced sludge biochar. Amine compounds can capture carbon dioxide well, and carbon dioxide molecules can chemically react with primary and secondary amines to form carbamates. It can promote the adsorption of carbon dioxide, thereby further improving the selective adsorption capacity of sludge-based biochar to carbon dioxide.

先进行一定程度的微波超声预处理,然后进行水热炭化反应,由于微波超声热解过程中,反应介质中有水存在,在促使物质热解效率提升的同时借助微波的加热效应和超声的空化作用之间产生的协同效应使热解物料在水热炭化过程中内部结构发生剧烈变化,从而使产物的孔隙结构更为丰富,进一步提升污泥基生物炭的比表面积和微孔结构。First, a certain degree of microwave ultrasonic pretreatment is carried out, and then the hydrothermal carbonization reaction is carried out. Due to the presence of water in the reaction medium during the microwave ultrasonic pyrolysis process, the heating effect of microwave and the empty space of ultrasonic are used to improve the pyrolysis efficiency of substances. The synergistic effect between the carbonization processes makes the internal structure of the pyrolysis material change drastically during the hydrothermal carbonization process, so that the pore structure of the product is more abundant, and the specific surface area and microporous structure of the sludge-based biochar are further improved.

在进行微波超声预处理前进行厌氧发酵,能够促使污泥和稻壳之间的混合程度提升,使二者融为一体,同时厌氧过程中污泥中的大分子物质发生了预分解,能够提升后续微波超声预处理的效率和效果,厌氧发酵结束后首先进行慢速搅拌,使物料进一步混匀,然后进行快速搅拌,向物料中引入大量气泡,在微波超声过程中,搅拌产生的气泡在超声条件下破裂产生的能量则作用于热解物料,进一步提升热解物料的内部孔隙率和比表面积。Anaerobic fermentation before microwave ultrasonic pretreatment can promote the mixing degree between sludge and rice husks, so that the two can be integrated. It can improve the efficiency and effect of the subsequent microwave ultrasonic pretreatment. After the anaerobic fermentation is completed, slow stirring is carried out to further mix the material, and then fast stirring is carried out to introduce a large number of air bubbles into the material. The energy generated by the rupture of bubbles under ultrasonic conditions acts on the pyrolysis material, further increasing the internal porosity and specific surface area of the pyrolysis material.

本发明制备的污泥基生物炭具有极大的比表面积和孔隙结构,同时富含二氧化硅成分且进行了氨基改性,从而使其在进行烟气中二氧化碳的吸附时具有极高的吸附量和吸附效率。The sludge-based biochar prepared by the invention has a large specific surface area and a pore structure, is rich in silicon dioxide and has been modified with amino groups, so that it has extremely high adsorption in the adsorption of carbon dioxide in flue gas. amount and adsorption efficiency.

具体实施方式Detailed ways

现详细说明本发明的多种示例性实施方式,该详细说明不应认为是对本发明的限制,而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。Various exemplary embodiments of the present invention will now be described in detail, which detailed description should not be construed as a limitation of the invention, but rather as a more detailed description of certain aspects, features, and embodiments of the invention.

应理解本发明中所述的术语仅仅是为描述特别的实施方式,并非用于限制本发明。另外,对于本发明中的数值范围,应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。It should be understood that the terms described in the present invention are only used to describe particular embodiments, and are not used to limit the present invention. Additionally, for numerical ranges in the present disclosure, it should be understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in that stated range is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

除非另有说明,否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料,但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入,用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时,以本说明书的内容为准。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention relates. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials in connection with which the documents are referred. In the event of conflict with any incorporated document, the content of this specification controls.

在不背离本发明的范围或精神的情况下,可对本发明说明书的具体实施方式做多种改进和变化,这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见得的。本发明说明书和实施例仅是示例性的。It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the present invention. The description and examples of the present invention are exemplary only.

关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等,均为开放性的用语,即意指包含但不限于。As used herein, "comprising," "including," "having," "containing," and the like, are open-ended terms, meaning including but not limited to.

本发明以下实施例中所使用的污泥源自某污水处理厂二沉池的活性污泥,浓缩后含水率为90%。The sludge used in the following examples of the present invention is derived from the activated sludge in the secondary sedimentation tank of a sewage treatment plant, and the moisture content after concentration is 90%.

实施例1Example 1

(1)将活性污泥和稻壳按照质量比10:4(该比例为污泥的干重和稻壳的质量比)混合后,按照料液比1g:10mL加水后,进行水热炭化反应(水热炭化条件:温度180℃,反应时间1h),得到炭化产物。(1) After mixing the activated sludge and rice husk according to the mass ratio of 10:4 (the ratio is the dry weight of the sludge and the mass ratio of the rice husk), after adding water according to the material-liquid ratio 1g:10mL, the hydrothermal carbonization reaction is carried out (Conditions for hydrothermal carbonization: temperature 180°C, reaction time 1h) to obtain a carbonized product.

(2)碳化产物与1mol/L的氢氟酸溶液混合(料液比1g:10mL)在60℃的温度下搅拌浸渍3h后用去离子水清洗过滤(将氢氟酸替换为盐酸、磷酸、醋酸、柠檬酸均可达到相似的技术效果)。(2) The carbonized product was mixed with 1 mol/L hydrofluoric acid solution (material-to-liquid ratio 1 g: 10 mL), stirred and immersed for 3 hours at a temperature of 60 °C, and then washed and filtered with deionized water (hydrofluoric acid was replaced by hydrochloric acid, phosphoric acid, Acetic acid and citric acid can achieve similar technical effects).

(3)步骤(2)产物置于乙二胺的乙醇溶液中(乙二胺质量分数为10wt%)浸渍(料液比1g:10mL)6h后离子水清洗过滤,100℃条件下真空干燥3h得到污泥基生物炭材料(将乙二胺替换为乙醇胺、二乙醇胺、三乙胺、乙胺均可达到相似的技术效果)。(3) The product of step (2) is placed in an ethanolic solution of ethylenediamine (the mass fraction of ethylenediamine is 10 wt%), immersed (material-to-liquid ratio 1 g: 10 mL) for 6 h, washed with ionized water, filtered, and dried under vacuum at 100 °C for 3 h Sludge-based biochar materials are obtained (replacing ethylenediamine with ethanolamine, diethanolamine, triethylamine, and ethylamine can all achieve similar technical effects).

实施例2Example 2

(1)将活性污泥和稻壳按照质量比10:3(该比例为污泥的干重和稻壳的质量比)混合后,按照料液比1g:10mL加水后,进行水热炭化反应(水热炭化条件:温度200℃,反应时间0.5h),得到炭化产物。(1) After mixing the activated sludge and rice husk according to the mass ratio of 10:3 (the ratio is the dry weight of the sludge and the mass ratio of the rice husk), after adding water according to the material-liquid ratio 1g:10mL, the hydrothermal carbonization reaction is carried out (Conditions for hydrothermal carbonization: temperature 200°C, reaction time 0.5h) to obtain a carbonized product.

(2)碳化产物与0.5mol/L的氢氟酸溶液混合(料液比1g:10mL)在40℃的温度下搅拌5h后用去离子水清洗过滤(将氢氟酸替换为盐酸、磷酸、醋酸、柠檬酸均可达到相似的技术效果)。(2) The carbonized product is mixed with 0.5mol/L hydrofluoric acid solution (material-to-liquid ratio 1g:10mL), stirred at a temperature of 40°C for 5h, washed with deionized water and filtered (replace hydrofluoric acid with hydrochloric acid, phosphoric acid, Acetic acid and citric acid can achieve similar technical effects).

(3)上述产物置于乙二胺的乙醇溶液中(乙二胺质量分数为10wt%)浸渍(料液比1g:10mL)12h后离子水清洗过滤,100℃条件下真空干燥3h得到污泥基生物炭材料(将乙二胺替换为乙醇胺、二乙醇胺、三乙胺、乙胺均可达到相似的技术效果)。(3) The above product was placed in an ethanol solution of ethylenediamine (the mass fraction of ethylenediamine was 10wt%), immersed (material-to-liquid ratio of 1g: 10mL) for 12h, washed with ionized water, filtered, and vacuum-dried at 100°C for 3h to obtain sludge Based on biochar materials (replacing ethylenediamine with ethanolamine, diethanolamine, triethylamine, and ethylamine can achieve similar technical effects).

实施例3Example 3

(1)将活性污泥和稻壳按照质量比10:2(该比例为污泥的干重和稻壳的质量比)混合后,按照料液比1g:5mL加水后,进行水热炭化反应(水热炭化条件:温度120℃,反应时间2h),得到炭化产物。(1) After mixing activated sludge and rice husk according to the mass ratio of 10:2 (the ratio is the dry weight of the sludge and the mass ratio of the rice husk), after adding water according to the material-to-liquid ratio of 1g:5mL, the hydrothermal carbonization reaction was carried out. (Condition of hydrothermal carbonization: temperature 120°C, reaction time 2h) to obtain a carbonized product.

(2)碳化产物与2mol/L的氢氟酸溶液混合(料液比1g:10mL)在50℃的温度下搅拌2h后用去离子水清洗过滤(将氢氟酸替换为盐酸、磷酸、醋酸、柠檬酸均可达到相似的技术效果)。(2) The carbonized product is mixed with 2 mol/L hydrofluoric acid solution (material-to-liquid ratio 1 g: 10 mL), stirred at a temperature of 50 ° C for 2 h, washed with deionized water and filtered (replace hydrofluoric acid with hydrochloric acid, phosphoric acid, acetic acid) , citric acid can achieve similar technical effect).

(3)上述产物置于乙二胺的乙醇溶液中(乙二胺质量分数为10wt%)浸渍(料液比1g:10mL)8h后离子水清洗过滤,100℃条件下真空干燥3h得到污泥基生物炭材料(将乙二胺替换为乙醇胺、二乙醇胺、三乙胺、乙胺均可达到相似的技术效果)。(3) The above product is placed in an ethanol solution of ethylenediamine (the mass fraction of ethylenediamine is 10wt%), immersed (material-to-liquid ratio of 1g: 10mL) for 8h, washed with ionized water, filtered, and vacuum-dried at 100°C for 3h to obtain sludge Based on biochar materials (replacing ethylenediamine with ethanolamine, diethanolamine, triethylamine, and ethylamine can achieve similar technical effects).

实施例4Example 4

同实施例1,区别在于,污泥的干重和稻壳的质量比为10:5。Same as Example 1, the difference is that the dry weight of sludge and the mass ratio of rice husk are 10:5.

实施例5Example 5

同实施例1,区别在于,污泥的干重和稻壳的质量比为10:1。Same as Example 1, the difference is that the dry weight of sludge and the mass ratio of rice husk are 10:1.

实施例6Example 6

同实施例1,区别在于,省略稻壳的使用。Same as Example 1, the difference is that the use of rice husks is omitted.

实施例7Example 7

同实施例1,区别在于,将水热炭化过程修改为传统管式炉热解炭化。Same as Example 1, the difference is that the hydrothermal carbonization process is modified to the traditional tube furnace pyrolysis carbonization.

实施例8Example 8

同实施例1,区别在于,省略酸溶液浸渍活化,仅进行有机胺溶液浸渍改性。Same as Example 1, the difference is that the acid solution impregnation activation is omitted, and only the organic amine solution impregnation modification is performed.

实施例9Example 9

同实施例1,区别在于,省略有机胺溶液浸渍改性,炭化产物进行酸溶液浸渍活化后直接进行真空干燥。The same as Example 1, the difference is that the organic amine solution impregnation modification is omitted, and the carbonized product is directly subjected to vacuum drying after being impregnated with an acid solution for activation.

实施例10Example 10

同实施例1,区别在于,省略酸溶液浸渍活化和有机胺溶液浸渍改性过程。Same as Example 1, the difference is that the acid solution impregnation activation and the organic amine solution impregnation modification process are omitted.

实施例11Example 11

同实施例1,区别在于,混合物在进行水热炭化过程前进行以下预处理:100r/min慢速搅拌30min混匀,然后600r/min快速搅拌3h,200℃微波超声(超声频率300Hz)预处理15min。The same as Example 1, the difference is that the mixture is subjected to the following pretreatment before the hydrothermal carbonization process: 100r/min slow stirring for 30min mixing, then 600r/min rapid stirring for 3h, 200 ℃ microwave ultrasonic (ultrasonic frequency 300Hz) pretreatment 15min.

实施例12Example 12

同实施例11,区别在于,仅进行微波预处理,省略超声条件。Same as Example 11, the difference is that only microwave pretreatment is performed, and ultrasonic conditions are omitted.

实施例13Example 13

同实施例11,区别在于,仅进行超声预处理,省略微波条件。Same as Example 11, the difference is that only ultrasonic pretreatment is performed, and microwave conditions are omitted.

实施例14Example 14

同实施例11,区别在于,混合物在进行微波超声预处理前进行以下预处理:50℃条件下厌氧发酵5天,100r/min慢速搅拌30min混匀,然后600r/min快速搅拌3h。The same as Example 11, the difference is that the mixture is subjected to the following pretreatment before microwave ultrasonic pretreatment: anaerobic fermentation at 50°C for 5 days, slow stirring at 100r/min for 30min, and then rapid stirring at 600r/min for 3h.

效果验证Effect verification

(1)实施例1-14所得污泥基生物炭的孔结构性能由物理吸附仪通过氮气吸脱附测试得到,吸附温度为77K。测试前先将污泥基生物炭进行预处理除去样品中的水汽和杂质气体。通过测得的氮气吸附等温线,进而计算得到吸附剂比表面积及孔容,结果见表1。(1) The pore structure properties of the sludge-based biochar obtained in Examples 1-14 were obtained by a physical adsorption instrument through nitrogen adsorption and desorption tests, and the adsorption temperature was 77K. Before the test, the sludge-based biochar was pretreated to remove the water vapor and impurity gas in the sample. Through the measured nitrogen adsorption isotherms, the specific surface area and pore volume of the adsorbent were calculated. The results are shown in Table 1.

(2)使用热分析仪检测污泥基生物炭在模拟烟道气中的二氧化碳吸附和解析性能,将15mg污泥基生物炭装入陶瓷坩埚中,通入氮气(50mL/min),并以10℃/min的速度加热至60℃保持120分钟,以除去空气中吸附的任何分子。随后将样品冷却至25℃,并在此温度下稳定60分钟。将氮气转换为15%CO2/85%N2的混合气体(50mL/min)进行CO2吸附,并保持15分钟以达到样品的饱和吸附平衡。最后,将气体再次转换为氮气(50mL/min),保持15min,用以脱除从混合气体中吸附的CO2。根据二氧化碳捕集过程中污泥基生物炭的重量变化来计算二氧化碳的吸附量,结果见表1。(2) Use a thermal analyzer to detect the carbon dioxide adsorption and desorption performance of sludge-based biochar in simulated flue gas, put 15 mg of sludge-based biochar into a ceramic crucible, pass nitrogen (50 mL/min), and use Heating at a rate of 10°C/min to 60°C for 120 minutes removes any molecules adsorbed from the air. The sample was then cooled to 25°C and stabilized at this temperature for 60 minutes. The nitrogen gas was switched to a mixed gas of 15% CO 2 /85% N 2 (50 mL/min) for CO 2 adsorption, and kept for 15 minutes to reach the saturated adsorption equilibrium of the sample. Finally, the gas was switched to nitrogen (50 mL/min) again for 15 min to remove the CO 2 adsorbed from the mixed gas. The adsorption capacity of carbon dioxide was calculated according to the weight change of the sludge-based biochar during the carbon dioxide capture process, and the results are shown in Table 1.

表1Table 1

样品sample 比表面积m<sup>2</sup>/gSpecific surface area m<sup>2</sup>/g 孔容,mL/gPore volume, mL/g CO<sub>2</sub>吸附量,mmol/gCO<sub>2</sub> adsorption capacity, mmol/g 实施例1Example 1 13171317 0.840.84 2.152.15 实施例2Example 2 12671267 0.810.81 2.072.07 实施例3Example 3 12581258 0.830.83 2.012.01 实施例4Example 4 10431043 0.750.75 2.242.24 实施例5Example 5 954954 0.640.64 1.851.85 实施例6Example 6 823823 0.550.55 1.741.74 实施例7Example 7 10171017 0.710.71 1.861.86 实施例8Example 8 908908 0.620.62 1.721.72 实施例9Example 9 10581058 0.720.72 1.831.83 实施例10Example 10 884884 0.570.57 1.651.65 实施例11Example 11 13041304 0.800.80 2.222.22 实施例12Example 12 11031103 0.750.75 2.042.04 实施例13Example 13 12311231 0.820.82 2.132.13 实施例14Example 14 14151415 0.910.91 2.422.42

由表1数据可以得出,本发明方法可以显著提升污泥生物炭的比表面积和孔容,提高其在吸附烟气中二氧化碳的吸附率。From the data in Table 1, it can be concluded that the method of the present invention can significantly improve the specific surface area and pore volume of the sludge biochar, and improve the adsorption rate of carbon dioxide in the adsorption flue gas.

以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention. within.

Claims (10)

1.一种污泥基生物炭,其特征在于,以污泥和稻壳的混合物为原料进行水热炭化,然后经过酸洗活化和氨基改性得到。1. A sludge-based biochar, characterized in that, taking the mixture of sludge and rice husks as raw materials for hydrothermal carbonization, and then obtaining through pickling activation and amino modification. 2.根据权利要求1所述的污泥基生物炭,其特征在于,所述污泥的干重和稻壳的混合质量比为10:(2-4)。2 . The sludge-based biochar according to claim 1 , wherein the dry weight of the sludge and the mixed mass ratio of the rice husks are 10:(2-4). 3 . 3.一种根据权利要求1-2任一项所述的污泥基生物炭的制备方法,其特征在于,包括以下步骤:3. A method for preparing sludge-based biochar according to any one of claims 1-2, characterized in that, comprising the following steps: (1)将污泥和稻壳混合得到混合物进行水热炭化得到碳化产物;(1) mixing sludge and rice husks to obtain a mixture and performing hydrothermal carbonization to obtain a carbonized product; (2)碳化产物首先置于酸溶液中进行浸渍,然后置于有机胺溶液中浸渍,然后真空干燥得到所述污泥基生物炭。(2) The carbonized product is first impregnated in an acid solution, then impregnated in an organic amine solution, and then vacuum-dried to obtain the sludge-based biochar. 4.根据权利要求3所述的污泥基生物炭的制备方法,其特征在于,所述步骤(1)中,水热炭化条件:温度120℃—220℃,时间0.5—2h。4 . The method for preparing sludge-based biochar according to claim 3 , wherein, in the step (1), the hydrothermal carbonization conditions are: temperature 120°C-220°C, time 0.5-2h. 5 . 5.根据权利要求3所述的污泥基生物炭的制备方法,其特征在于,所述步骤(2)中,所述酸溶液的溶质为盐酸、磷酸、醋酸、柠檬酸、氢氟酸中的一种或多种,溶剂为去离子水,浓度为0.5—2mol/L,浸渍时间为2—6h,温度40℃—60℃;所述有机胺溶液的溶质为乙二胺、乙醇胺、二乙醇胺、三乙胺、乙胺,溶剂为乙醇,有机胺溶液浓度为5-15wt%,浸渍时间为6-12h。5 . The method for preparing sludge-based biochar according to claim 3 , wherein in the step (2), the solute of the acid solution is hydrochloric acid, phosphoric acid, acetic acid, citric acid, and hydrofluoric acid. 6 . The solvent is deionized water, the concentration is 0.5-2mol/L, the immersion time is 2-6h, and the temperature is 40℃-60℃; the solute of the organic amine solution is ethylenediamine, ethanolamine, diamine Ethanolamine, triethylamine, ethylamine, the solvent is ethanol, the concentration of the organic amine solution is 5-15wt%, and the immersion time is 6-12h. 6.根据权利要求3所述的污泥基生物炭的制备方法,其特征在于,所述步骤(1)中,所述混合物在水热炭化前进行以下预处理:慢速搅拌混匀后快速搅拌3-5h,微波超声预处理10—20min。6 . The method for preparing sludge-based biochar according to claim 3 , wherein, in the step (1), the mixture is subjected to the following pretreatment before hydrothermal carbonization: stirring and mixing at a slow speed and then quickly Stir for 3-5h, microwave ultrasonic pretreatment for 10-20min. 7.根据权利要求6所述的污泥基生物炭的制备方法,其特征在于,所述慢速搅拌转速为100-150r/min,所述快速搅拌转速500-600r/min,微波超声预处理温度100℃—250℃,超声频率300-500Hz。7. The method for preparing sludge-based biochar according to claim 6, wherein the slow stirring speed is 100-150 r/min, the fast stirring speed is 500-600 r/min, and the microwave ultrasonic pretreatment Temperature 100℃-250℃, ultrasonic frequency 300-500Hz. 8.根据权利要求6所述的污泥基生物炭的制备方法,其特征在于,所述混合物在进行微波超声预处理前进行以下预处理:40-50℃条件下厌氧发酵3-5天,慢速搅拌混匀后快速搅拌3-5h。8 . The method for preparing sludge-based biochar according to claim 6 , wherein the mixture is subjected to the following pretreatment before microwave ultrasonic pretreatment: anaerobic fermentation at 40-50° C. for 3-5 days. 9 . , Slowly stir and mix well, and then stir quickly for 3-5h. 9.一种根据权利要求1-2任一项所述的污泥基生物炭在吸附二氧化碳方面的应用。9. An application of the sludge-based biochar according to any one of claims 1-2 in adsorbing carbon dioxide. 10.根据权利要求9所述的应用,其特征在于,在吸附燃烧后烟气中二氧化碳中的应用。10. The application according to claim 9, characterized in that, the application in adsorbing carbon dioxide in flue gas after combustion.
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